Mining industry has been identified as the main sustenance of the South African economy, however the negative impacts of the industry on the ecological systems cannot be over emphasized due to the released waste which is mostly heavy metals into the environment. The study evaluated six heavy metal (A1, Cu, Fe, Ni, Pb and Cr) contents in a tailings dam from a specific mine site. Two sets of samples for the investigation were measured, that is, one in year 2012 and the other in year 2013. In the year 2012, the sample set was only taken at a distance profile of 500 meters from the foot of the dam, whereas the sample set taken in the year 2013 was for the 500 and 1500 meter distance profiles from the foot of the dam. The year 2012 and 2013 sample sets for the 500m distance profile were sampled very similarly to each other. A kilogram of each sample was taken as per grid format. The samples at varied depths were taken at 0-cm depth for the top layer, 20cm depth for the second layer, and 30cm depth for the third layer. The samples for the surface varied distance were taken at 1 m, 2m, 3m, and 4m away from each 500m and 1500 sampling points. The 2012 samples were analysed using characterization methods namely ICP MS and The 2013 samples were analysed using the ICP OES. The comparison of the field results for the six heavy metals studied (A1, Fe, Pb, Cu, Ni and Cr) was performed using statistical analytical methods, namely ANOVA. The statistical analysis results for heavy metals (A1, Fe, Pb, Cu, Ni and Cr) from sample and 2013 revealed that the group means are not significantly different from each other which means that there is no significant difference in (A1, Fe, Pb, Cu, Ni and Cr) concentrations with respect to both depth and distance. The observations from both 2012 and 2013 indicate the results of the samples are in agreement. In addition, the comparative average concentrations of the three results obtained reach the same conclusion that the tailing dam probably does not introduce considerable or significant amounts of these metals (A1, Fe, Pb, Cu, Ni and Cr) into the surrounding soils. / Chemical Engineering / M. Tech. (Chemical Engineering)

We initially studied the treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron as the electron donor. The results demonstrate that this electron donor can serve as the sole exogenous slow-release electron donor to drive sulfate reduction over 400 operational days at short HRTs (1-3 days). The synthetic acid rock drainage contained high heavy metal concentrations (up to 50 mg/L of copper) and pH values ranging from 3.0 to 7.0. Treatment of this acid rock drainage efficiently removed Cu, Cd and Pb (>99.7%) and increased pH to circumneutral values (7.3-7.7). Elemental analysis indicated that formation of insoluble metal sulfides was responsible for the effective metal removal in the zero valent iron columns. In the second study, three inoculated columns containing anaerobic granular sludge were fed a synthetic medium containing H₂SO₄ and Cu²⁺ during the experimental period of 4 months. Algae biomass promoted 80% of sulfate removal (12.7 mg SO₄²⁻ d-1), enabling near complete Cu removal (>99.5 %), and alkalinity generation, raising the effluent pH to 6.5. In the algae amended columns Cu²⁺ was precipitated with biogenic H2S produced by sulfate reduction. Whole cell algae and lipid extracted algae biomasses were both shown to be effective e-donors in driving sulfate reduction of ARD, thus enabling the precipitation and removal of Cu²⁺. The precipitate retained in the columns was composed mostly of insoluble copper sulfide formed from the biogenic sulfide, as shown by sequential extraction and X-ray diffraction. In the third study, several pretreatments, i.e., thermal, chemical, sonication and combinations thereof, that enhance anaerobic biodegradability of Chlorella protothecoides biomass were evaluated. The results demonstrate that anaerobic digestion of pretreated Chlorella protothecoides biomass generates energy-rich methane and recovers nitrogen nutrients. Sonication of algal biomass under optimized conditions provided a significant increase in the methane yield (327 mL STP CH₄ g⁻¹ VS) compared to untreated algae (146 mL STP CH₄ g⁻¹ VS), as demonstrated in anaerobic digestion experiments incubated for 41 days. In contrast, thermal pretreatment provided only a moderate increase of the methane yield and alkaline treatment led to a decrease of the methane yield compared to the untreated algal biomass. Additionally, sonication treatment provided a 4.1-fold increase in the release of ammonia nitrogen during anaerobic digestion of the algal biomass. In the fourth study, the nutrient recovery and biogas generation from the anaerobic digestion of waste biomass from algal biofuel production was investigated. Anaerobic digestion of whole cell and lipid extracted Chlorella sorokiniana-1412 released 48.1 and 61.5% of the total algal nitrogen as NH₄⁺-N, and 87.7 and 93.6% of the total algal P as soluble P, respectively. The biochemical methane potential, quantified through the methane yield of whole cell algae and lipid extracted algae, was 0.298 and 0.253 L methane/g algal volatile solids, respectively. The conversion of lipid extracted algae and whole cell algae biomasses to methane was very similar (38 and 41% on a COD basis, respectively), indicating that the energy yield was not significantly lowered by extraction of the lipid fraction (which accounted for 9% of algal dry weight). Sonication improved the access of hydrolytic enzymes to algal biopolymers, compensating in part for the energy lost due to lipid extraction. The above results demonstrate that algal waste from the biodiesel industry has the potential to be recycled through anaerobic digestion into valuable nutrients and energy. These studies indicate that zero valent iron and algae biomass are promising reactive materials for the treatment of acid rock drainage in sulfate-reducing permeable reactive barrier systems. Additionally, to promote algae cultivation for the biodiesel industry, the anaerobic digestion of algae residues can generate nutrients and energy, making algae cultivation more fiscally attractive.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / This thesis reports on an exploratory investigation of proposed sludge guideline limits of heavy metal (cadmium, chromium, copper, nickel, lead and zinc) concentrations for South Africa. The purpose of the study is to determine allowable heavy metal concentrations in sludge for use as fertilizer in agriculture that can be attained and is practically possible without being detrimental to the environment. This determination was done by investigating the potential sources and concentrations of these heavy metals at the Potsdam Wastewater Treatment Works (WWTW) and also the efficiency of the treatment works in removal of these heavy metals. A heavy metal mass balance of both the influent at the Potsdam WWTW and the wastewater through the treatment works was calculated. This study also proposes possible interventions to minimize the levels of these heavy metals. Results for the heavy metal mass balance of the influent showed that a large quantity of some metals were unaccounted for, this implies that either industries discharge illegally after hours or the present monitoring undertaken by the City of Cape Town is inadequate. The large percentage of unaccounted cadmium suggests another source, which should be further investigated. The mass balance of the wastewater through Potsdam WWTW concluded that all these heavy metal limits were attainable, and that in some cases can be lowered even more. The treatment works has a high removal efficiency of these heavy metals, and a substantial reduction of these limits is justified. In the period of this study, the area under investigation gradually expanded, as more industries were established in it. Although the works was performing beyond its capacity it nevertheless was able to attain the rigorous heavy metal limits in sludge that are envisaged. There has also been a reduction in limits of heavy metals for discharge of final effluent into waterbodies; this study shows that these limits are also attainable.

Potentially harmful elements (PHEs) have been researched in a wide variety of disciplines, including pedology, chemistry, pollution science and medicine. Within the scientific community, emphasis has usually been placed on the toxic elements, such as cadmium, chromium, lead and arsenic, but rarely has there been consideration of interactions between PHEs, the sediment matrix and processes occurring in the sediments. Dredging of canals is needed for navigability purposes and consequently testing of dredged sediments (to assess whether sediments are hazardous) and landfilling can be costly for British Waterways facing constantly changing regulations and reduction in government grants. PHE mobility and availability in canal sediments can be affected by oxygen availability, pH and Redox. Remediation is thus becoming a priority for British Waterways to limit their operational costs. Zeolites, a type of remediation tool, have been widely studied in the past 30 years due to their attractive properties, such as molecular-sieving, high cation exchange capacities and their affinity for PHEs. The pilot study to investigate the efficiency of the clinoptilolite showed that there was a concentration difference between PHEs adsorbed by the clinoptilolite and the PHE concentration lost from the sediments from three sites in the West Midlands. Thorough characterisation of the sediments was needed to understand the speciation of the PHEs and the secondary processes occurring in the sediments. The different components of the sediments were analysed using various analytical methods, such as X-Ray Fluorescence spectroscopy (XRF), particle size and X-ray Diffraction (XRD) for the solid-inorganic phase, Ion Chromatography (IC) and Inductively Coupled Plasma-Optical Emissions Spectroscopy (ICP-OES) for the liquid phase (pore water), Gas Chromatography-Mass Spectrometry (GC-MS) and organic loss on ignition for the organic phase, pH and Redox for the electrochemistry of the sediments and Scanning Electron Microscope with Energy Dispersive X-Ray analysis (SEM-EDX) for microscopy and imaging. The British Geological Survey (BGS) sequential extraction method was used to investigate the different phases in the sediments. pH remained near neutral for all three sites and Redox remained anoxic. Organic contents for all three sites were around 30% and contained most of the polycyclic aromatic hydrocarbons considered hazardous. Pore water showed only high concentrations of sulphates but low concentrations of PHEs, suggesting PHEs were not mobile. Sequential extraction confirmed the other results showing that PHEs were mainly associated with stable phases, such as iron and manganese oxides or sulphides. The results have been taken into consideration to design a new remediation strategy to maximise efficiency of the zeolite.

published_or_final_version / Ecology and Biodiversity / Master / Master of Philosophy

<p>Ensåsengruvan is a mine situated within Ljusdals municipality in central Sweden. Themine was in use from 1984 to 1991 and has since been undergoing a remediation program. Mine tailings from sulfide rich ore is a potential environmental hazard due to its tendency to cause acid waters and heavy metal leakage. Lake Ensjön is situated one kilometer from the mine area. Due to the hydrological conditions it was not expected to receive inflowing water from the mining area. A study done in 2005 showed high amounts of heavy metals in the lake.</p><p>In this study water and sediments was analyzed to confirm the results from the 2005 study. Water was sampled two times during summer 2006 from the lake and adjoining streams. Sediment samples were collected with a core sampler at ten different locations within the lake. The water and sediment samples were analyzed for heavy metal content. Sub-samples from different depths in the sediment core were extracted so that conclusions on the contamination history could be drawn. The sediments were dated trough Cs-137 analyses. The depth in the profile with the highest Cs-137 content can be dated to the time of the Chernobyl fallout (1986). After dating, relevant samples were analyzed for metal content.</p><p>The results show that Ensjön is contaminated by a local source. The surface sediments are high in copper, zinc, nickel and cadmium content. The content is high both compared to the samples from deeper in the sediment core and the surface sediments analyzed in the reference study done in 1980. The amounts of heavy metals are also high relative to the standards set by the Swedish Environmental Protection Agency. The water from the stream adjoining the lake from the mining area is high in content of the previously mentioned metals. The methods used, including sediment dating and metal analyses together with water analyses, has proven to be useful in investigating a suspected contamination from a point source.</p><p>It can be concluded that Lake Ensjön is contaminated with water from the mine waste. No other sources in the catchment area can be the source of the enriched amounts of heavy metals. Focus should in further work be put upon finding the exact source of leakage from the mining area.</p> / <p>Från Enåsengruvan i Ljusdals kommun utvanns ur sulfidmalm guld, silver och koppar under åren 1984 till 1991. Avfall från sulfidmalmsgruvor medför miljöproblem genom försurning och läckage av tungmetaller. Vanligtvis täcks avfallet med jordmassor eller vatten för att förhindra påverkan på naturen. De studier som genomfördes under prospekteringen visade på att Ensjön, som är belägen inom en kilometers avstånd från gruvområdet, inte skulle påverkas av gruvan men en provtagning under 2005 visade på höga halter av tungmetaller i sjön.</p><p>I denna studie har Ensjöns vattenkvalitet undersökts genom vatten och sedimentanalyser. Vattenprover i sjön och dess inlopp togs två gånger under sommaren 2006 och sedimentprover togs vid ett tillfälle på tio olika lokaler i sjön. En djupprofil av sedimenten analyserades för att föroreningshistoriken från innan gruvan togs i bruk till nutid skulle kunna kartläggas. För att datera sedimenten analyserades de med avseende på Cs-137. De högsta halterna av Cs-137 kan härledas till nedfallet från Tjernobylolyckan 1986. Efter datering valdes lämpliga prover ut för metallanalys.</p><p>Resultaten visar på förhöjda halter av koppar, zink, nickel och kadmium. Halterna i ytsedimenten är höga både jämfört med de halter som återfinns på större djup i sedimentprofilen, motsvarande avsättning innan gruvdriften och vad som uppmättes i referensstudien från 1980. Halterna är även höga relativt de jämförvärden som Naturvårdsverket satt upp. Vattenanalyserna visar på att vattnet i inflödet från gruvområdet innehåller höga halter av de tidigare nämnda metallerna. Metoden med Cs-137-datering och analys med avseende på metaller av sediment har visat sig fungera väl för kartläggning av en nutida förorening från en punktkälla. Tillsammans med kompletterande vattenprover ger det en bra bild av den rådande situationen.</p><p>Då resultaten visar att Ensjöns vatten är påverkat av en punktkälla och alla andra källor kan uteslutas får det anses klarlagt att sjöns vatten är påverkat av dränagevatten från gruvområdet. Fortsatta studier bör fokusera på att klarlägga den exakta källan till läckaget från gruvområdet.</p>

<p>Four different kinds of filter-materials with reactive surfaces have been studied concerning their capacity to absorb heavy metals in leachate from a municipal waste deposit. The heavy metals studied were: lead, cadmium, copper, mercury, chromium, nickel and zinc. The leachate contains high levels of dissolved organic carbon (DOC) and has a high pH-value along with a high buffer capacity. These characteristics of the leachate make it difficult to remove pollutants and require efficient filters. The filters that were examined in the report are blast-furnace slag with CaO, sand covered with iron oxides, olivine and nepheline. The experiment was carried out in two sets, starting with batch experiments followed by a column study. The objective of the batch experiments was to find out how variations in pH affected the sorption capacity of the materials. The interval used during the test was from pH 5 to pH 10. The computer program VisualMinteq was used to evaluate the dominating sorption processes when the materials interacted with the solutions. Two different kinds of solutions were used in the batch experiment. One of them was the leachate, to which known concentrations of heavy metals were added (about 1 μM) and the other consisted of sodium nitrate, a solution without organic compounds, which was used as a reference. The sodium nitrate solution was also spiked with the same concentration of heavy metals as the leachate.</p><p>The results from the batch experiment showed that the sorption of heavy metals was lowered if the DOC level was high. No relation between pH and sorption ability could be found for the leachate, but for some metals in the sodium solution a higher pH improved the removal of heavy metals. The two materials that showed best results in the batch experiment were the blast-furnace slag and the sand with iron oxides. These materials were used in the column study. The olivine material was somewhat better than the nepheline in the batch experiment.</p><p>Four columns were used in the column study, two for each material. Leachate with heavy metals was pumped into the columns with a specific flow rate; at first a low flow rate was used and when half the experiment time had passed the flow rate was increased. The flow rates used were 0.12 m/24 h and 0.62 m/24 h. The outcome of the column experiment showed that the slag had the highest ability to adsorb metals. The metal sorption was over 60 percent for lead, cadmium and zinc, where the highest sorption was obtained for lead. No affects were noticed when the flow rate was increased.</p> / <p>I detta examensarbete har fyra olika reaktiva filtermaterials kapaciteter att ur deponilakvatten avskilja tungmetallerna bly, kadmium, koppar, kvicksilver, krom, nickel och zink testats. Deponilakvatten är ett avloppsvatten med höga halter organiskt material (DOC), högt pH och en hög buffertkapacitet. Dess sammansättning ställer stora krav på ett filter och närvaron av ligander påverkar sorptionprocesserna. Filtren som ingått i studien är kalciumoxiddopad masugnsslagg, järnoxidtäckt sand, olivin och nefelin.</p><p>Försöken utfördes i två delar, med inledande skakförsök och därefter kolonnförsök. I båda försöken användes lakvatten med en extra tillsats av tungmetaller. I skakförsöken användes även natriumnitrat; ett referensvatten utan organiska ligander, även det spikat med tungmetaller. I skakförsöken studerades avskiljningens pH-beroende för de olika filtren, med ett pH-intervall på ca 5 – 10. Därefter modellerades resultaten i jämviktsprogrammet VisualMinteq för att fastställa vilka processer som styr avskiljningen. Skakförsöken och kolonnförsöken utfördes båda i klimatrum vid 8 ºC, för att efterlikna markens naturliga temperatur.</p><p>Resultaten från skakförsöken visade att masugnsslagg och järnoxidsand gav bäst avskiljning för de flesta tungmetaller. Olivin och nefelin var sämre metallsorbenter, där olivin uppvisade något bättre resultat än nefelin. Inget tydligt pH-beroende för lakvattnet kunde utläsas, men för natriumnitratlösningen gav en pH-höjning en ökad sorption för vissa metaller. Den kemiska jämviktsmodelleringen visade att den dominerande processen i filtermaterialen var sorption på filterytorna. De två filtermaterialen som visade bäst resultat i skakförsöken (slagg och järnoxid) studerades vidare i kolonnförsök, där ett bestämt lakvattenflöde pumpades genom kolonner packade med materialen. Två olika flödeshastigheter testades (0,12 m/dygn och 0,62 m/dygn) och sorptionen av metaller analyserades. Slaggen uppvisade högst avskiljningskapacitet av de studerade filtren. De metaller som sorberades bäst var bly, kadmium och zink (över 60 % avskiljning), där den högsta sorptionen erhölls för bly. Gemensamt för både skak- och kolonnförsöken var att sorptionen försvårades då halten organiskt material (DOC) ökade, vilket beror på att DOC konkurrerar med de reaktiva ytorna på filtren om att binda den fria metalljonen. Ingen minskande avskiljningseffekt av en flödesökning kunde utläsas.</p>

No description available.

<p>X-ray fluorescence (XRF) detection of heavy metals is a cost- and time-effective method for investigation of polluted areas. Compared to laboratory analysis, XRF analysis is limited by high detection limits and uncertainties in some situations. Preparation of samples is known to affect the results of measurements.</p><p>The purpose of this thesis is to bring a deeper understanding of how different factors affect the results of XRF-analysis. A large number of measurements have been made with the instruments Niton XLt 700 and Niton Xli 700. Results from measurements of lead, zinc and copper have been analysed.</p><p>This study has shown that a greater moisture content will give a lower measured concentration for the same sample. If the moisture content is known, it is possible to make good approximations of concentrations in dry samples. No obvious differences were found between different metals.</p><p>Proper homogenisation of samples was found to be one of the most critical issues. It should be noted that laboratories do not usually homogenise samples prior to analysis, so samples sent for laboratory verification should therefore be homogenised before sending.</p><p>Sample preparation, including drying, sieving to finer grain-sizes and analysing in a special sample cup was found to increase the measured concentrations and decrease the variation between measurements. The concentrations differed with different sample matrices and with sample preparation. Because of the differences, measurements should always be correlated with laboratory analysis before any conclusions can be made. In situations when metals are well within detection range of the XRF instrument, the only preparation needed is in most cases homogenisation. If metal levels are just at the limit, or just below the detection limit, further preparations of samples should be made. When drying samples makes detection possible, more preparation is usually not worth the effort. If detection limits still are a problem after drying, the samples should be sieved and analysed in sample cups. In situations where concentrations still are below the</p><p>detection limit when analysing in sample cups, or if the measurements are disturbed for other reasons, another method than XRF-analysis must be used. When XRF analysis is possible, the method is preferable compared to only laboratory analysis. This cost- and time effective method makes a larger number of measurements possible, and gives a more complete overview of a polluted area.</p> / <p>Analys med röntgenfluorescensdetektor (XRF) är en snabb och kostnadseffektiv fältmetod för detektion av tungmetaller i mark. Nackdelen är att mätningarna inte är tillförlitliga i alla sammanhang och att detektionsgränsen för många ämnen är förhållandevis hög. Det är sedan tidigare känt att olika former av provbearbetning påverkar mätresultaten.</p><p>I detta examensarbete har undersökts hur olika faktorer påverkar mätresultaten vid analys av jordprover med XRF instrument. Faktorerna som undersökts är inverkan av vattenkvot, kornstorlek, provpåsar och olika provbearbetningsmetoder. Vid provbearbetningsförsöken skickades prover även in till externt laboratorium för jämförande analys. Metaller som undersökts är bly, zink och koppar.</p><p>Vid undersökningen konstaterades att en ökad vattenkvot ger upphov till lägre mätvärden. Vid kännedom om vattenkvot kan halt per torrsubstans med god överensstämmelse uppskattas utifrån mätningar på fuktiga prov. Är precisionskraven stora och vattenkvoten varierande och okänd bör dock proverna torkas innan mätningar görs. Ingen avsevärd skillnad sågs mellan de olika metaller som undersöktes.</p><p>Vid undersökningen om provbearbetningens betydelse visade det sig att homogeniseringen av proverna är mycket viktig, inte minst av prover som skickas till laboratorieanalys.</p><p>Ökad provbearbetning med torkning och siktning till mindre kornstorlek tenderar att ge högre mätvärden med XRF instrument. Storleksmässigt är mätvärden vid obearbetade prov mest överensstämmande med laboratorieanalys. Mest skiljer sig analys på finsiktade prover i provkopp. Korrelationsmässigt finns i en del fall en tendens till bättre överensstämmelse med mer bearbetade prov. Den största vinsten med ökad bearbetning av prover konstaterades i detta arbete vara att mark med lägre metallkoncentrationer då kan analyseras.</p><p>I de fall där halterna av metaller ligger väl inom XRF instrumentets detektionsområde visade det sig att det oftast är tillräckligt att endast homogenisera proverna innan analys görs. I de fall där koncentrationen av metaller är på gränsen till vad XRF instrumentet kan detektera rekommenderas att proverna torkas, eller om nödvändigt torkas, siktas och analyseras i provkopp. Där nivåerna av metaller ligger under detektionsgränsen för XRF instrument trots provbearbetning, eller där andra ämnen till exempel järn stör mätningarna, måste en annan analysmetod väljas.</p>

Current concerns about inorganic contaminants in food products have raised consumer awareness of anthropogenic sources of heavy metal contamination in ecosystems and their potential threat to human health. Mining and exploration of mineralized zones is a major source of such contamination. Mining throughout the Patagonia Mountains, Arizona, has left a legacy of surface water contamination by acid mine drainage (AMD). This study assessed the impacts of AMD on soils and plants throughout the study area. Concentrations, transport, and loading of heavy metals (Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, and Zn) in soils and plants was quantified using total concentrations, suggested toxic levels, and plant and soil pollution indices. Pollution indices were modified to include antimony and molybdenum. Pollution indices greater than 100 were found in areas disturbed by mining, remediation sites and beyond. Cattle grazing on grasses contaminated by metals were documented.